Method of treating hydrocarbons



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W. M. CROSS METHOD OF TREATING HYDROCARBONS Original Filed June 1, 1915 March 1, 1932.

an M OR O O O O O O O O Patented Mar. 1, 1932 UNITED STATES PATENT OFFICE WALTER M. CROSS, OF KANSAS CITY, MISSOURI, ASSIGNOR, BY MESNE ASSIGNMENTS,

TO GASOLINE PRODUCTS COMPANY, INC., OF WILMINGTON, DELAWARE, A CORPO- BATION OF DELAWARE METHOD or 'rnnarme HYDROCARBONS.

Original application filed June 1, 1915, Serial No. 31,436, renewed January 4, 1922, Serial No. 527,049. Divided and this application filed April 8, 1927. Serial No. 182,149.

This invention relates to improvements in method of treating hydrocarbons and products derived therefrom and more particularly to a process by means of which gasoline and other low boiling point hydrocarbons can be produced from residuum, distillate slops and kerosene.

This application is a division of my copending renewal application Serial No. 527,049, originally filed June 1, 1915 as Serial No. 31,436.

Among the salient objects of the invention are to provide a process adapted for economically and efiiciently changing heavy unmarketable hydrocarbons into gasoline or other readily marketable hydrocarbons; to provide a process in which the noncondensable gases can be removed from the apparatus during treatment and the remaining products of conversion retained in the apparatus and subjected to the pressure and temperature desired; to provide a process in which the noncondensable gases can be intermittently or continuously taken off and used as fuel for both heating and power purposes either in running this apparatus or others; to provide a process in which the hydrocarbons treated are subjected in anearly closed vessel to comparatively hightemperature and pressure and the treatment continued for a length of time sufficient to permit the products of conversion to become stable; to provide a method of treating hydrocarbons in a nearly closed vessel in which the percentage of yield of gasoline or other desired product is increased by the removal of the noncondensable geases so as to provide greater vapor space for the condensable gases; and in general to provide a new and improved process for producing gasoline or other marketable hydrocarbons from residuum, kerosene or other hydrocarbons which may be unmarketable.

In the drawing:

The single figure is a side elevation of an apparatus capable of carrying out my process.

In the particular embodiment of my invention shown in the drawing, and describing first in detail the apparatus, 1 designates a furnace, in which is located a series of tubes 2, connected to a hollow end plate 3. Opening into the lower portion of the end plate 3 is an inlet at connected to a source of supply in a manner hereinafter described in detail and at its upper end the hollow plate 3 is connected by a conduit 5 with a converter tank 6. Leading from the latter at a plane below that of the end 7 of the pipe 5 is a pair of discharge pipes 8 and 9, the former of which forms a discharge conduit for the treated product. The pipe 9 is connected by a T- coupling 10 to the supply pipe 11, and the inlet pipe 4. The latter is provided with a rotary pump 12 driven by a motor 13, both of which are mounted on a common base 15. Communication between the pipes 9 and 4 is controlled by a shutoff valve 16, and a similar shutoff valve 17 is employed for shutting ing started the oil in the pipes 2 will heat and is circulated from the converter tank to the heating pipes and back by means of the pump 12 which forces the oil to circulate rapidly through the entire apparatus. As the temperature increases vapor starts to come off from the body of the oil and accumulates in the converter tank 6, and as there is no means for the condensable gases to escape, it is obvious that the pressure in the apparatus will also rise. The process above described is carried on until the temperature reaches the point at which the hydrocarbons formed of relatively heavy molecular weight break up into a much larger number of hydrocarbons of relatively small molecular weight. The temperature at which this reaction occurs varies with different hydrocarbons. At a temperature of between 750 to 1,000 F. substantial cracking will almost invariably occur. hen this temperature is reached it will be noticed that there is an excessive rise in pressure relative to the rise in temperature and it is at or just slightly above this temperature that the process is continued until the products of conversion get into equilibrium so that there would no longer be an excessive rise in pressure in proportion to the rise in temperature.

During the generation of the vapors there is a large amount of noncondensable gases formed which naturally increase the pressure and interfere with the conversion products coming off of the liquid. I have, therefore, provided means for permitting the escape of the noncondensable gases, that is, those gases which :are not condensable at degrees C. The apparatus for the escape of the gases is as follows Leading, from the upper end of the converter tank 6 is a pipe 18 having an elbow fitting 19, to one 'side of which is connected a Weighted safety valve 20. At its upper end this pipe 18 is connected to a condensing coil '21 which passes through a cooling tank 22 and at its outer end discharges into the pipe 23. Water or other suitable cooling medium is supplied to the tank 22 through an inlet 24 and discharged through an outlet 25 in the usual manner. By regulating the temperature of the cooling medium and the size of the opening through which the gases must pass, it is possible to discharge into the pipe 23 only those gases which are noncondensable at any predetermined temperature.

However, I preferably regulate the condensing action so that only the noncondensable gases suitable for illuminating or heat ing purposes are'permitted to pass into the pipe 23. As shown in the drawing, this pipe has an elbow 26 into which connect pipes 27 and '28. The latter forms a connection with the gas storage tank 29 and also with the furnace pipe 30. Suitable shutoff valves 31, 32, .33, and 34 control the passage of the gas through the various pipes. When the shutoff valve 34: is opened and the valves 32 and 33 closed, the gas can be conducted through the pipe 27 to the burner or other apparatus employed in the refinery or conducted away for any other use. However, I preferably employ a portion of the gas escaping past the condenser, as a fuel supply for the furnace I.

This process whereby the noncondensable gases are permitted to escape from the otherwise closed apparatus is an important feature of my invention. It has been found by actual test that the percentage of gasoline secured in a single treatment of the hydrocarbons in the converter 6 is increased about 10% by permitting the non-condensable gases to escape.

In use, the apparatus is filled as previously described, and the residuum or other oil subjected to heat until the pressure gauge 35 shows that the pressure is rising rapidly. The operator then opens the Valve 33 and permits the escape of the noncondensable gases. This valve 33 can be opened and closed at intervals or it can be just slightly cracked so that the escape of gases while continuous is sufliciently slow to permit the escape in proportion to their formation. By increasing the size of the opening and changing the condensing temperature it would be possible to also take off gasoline or any other light hydrocarbon. The apparatus is hoW- over preferably so proportioned and regulated that only the normally noncondensable gas-es can escape, as this permits the condensable gases being retained in contact with those in the liquid phase a su'flicient length of time to destroy any free olefines'. The removal of the noncondensable gases allows the condensable gases a larger space in which to accumulate while the process is being carried out.

After the heating and circulating of the liquid has been continued until the process is finished, the resultant product is drawn off through the outlet pipe 36 to a still. The completion of the process is readily determined by those skilled in the art. The proc ess is completed when the hydrocarbons have been subjected to the reacting conditions sufliciently long to convert a substantial proportion of the heavy hydrocarbons to lighter hydrocarbons. The time of treatment, of course, will vary with the oil used. The product of this conversion process will, if the heat treatment has been continued long enough, then be conducted to the still and subjected to the same treatment that the crude oil is in refining. If the treatment in the converter 'has'been continued far enough a relatively large percentage of gasoline having an end point of 300 F. will be formed. I Vhilc I have described the process with reference to making gasoline from residuum, it is obvious that kerosene, distillate slops and various other hydrocarbon compounds could be treated to produce any desired lighter conversion product. The details of construction of the apparatus could also be changed and I do not desire tolimit the invention except as specified in the appended claims.

I claim:

1. The described converting process for the treatment of heavy hydrocarbons which consists in confining a bulk supply of liquid with a vaporous space thereabove, passing the material in a fine stream from the bulk 139 supply through a cracking zone and back to the bulk supply while maintaining thereon the pressure of substantially all of the condensable vapors generated during said treatment, passing the generated incondensable and entrained condensable products from the vapor space and subjecting the same to a condensing action, returning to the bulk supply the condensates from said condensing action and conveying away the incondensable gases.

2. The process of cracking hydrocarbon oil, which comprises converting the oil in a restricted stream and enlarged chamber, the restricted stream only being heated, and the enlarged chamber containing during the conversion of the'oil therein, a substantial body of liquid oil under the pressure of the gases and vapors evolved from the oil, retaining the oil in the system until a condition of substantial equilibrium is reached, regulating the pressure upon the liquid oil by venting the upper portion of the chamber, and withdrawing the products of conversion from the enlarged chamber.

3. Aprocess of converting hydrocarbons, which comprises heating and digesting the oil in a coil and enlarged chamber, the coil only being heated, maintaining a substantial body of liquid oil in the enlarged chamber under the pressure of a substantial body of gases and vapors evolved from the oil to form liquid and vaporous products of conversion each containing substantial amounts of the constituents of gasoline, regulating the pressure upon the liquid in the enlarged chamber by the discharge of volatile products therefrom, and withdrawing the liquid and vaporous products of conversion from the enlarged chamber through a common outlet.

4. A process of converting hydrocarbon oil which comprises heating and digesting the oil in a coil and enlarged chamber, the coil only being heated, maintaining a body of liquid oil in the enlarged chamber under the pressure of gases and vapors evolved from the oil, discharging gases and vapors from said enlarged chamber to a condenser, condensing and returning condensable vapors to the enlarged chamber for further treatment, regulating the pressure in the enlarged chamber by the discharge of uncondensed products from the condenser, and withdrawing liquid and vaporous products of conversion from the enlarged chamber through a common outlet.

5. The process of subjecting petroleum oils to pyrogenesis which consists in heating a body of relatively heavy oil to a decomposing temperature, maintaining such temperature for a suflicient time to effect a substantial conversion of the oil body into lighter hydrocarbons, and relieving the pressure within the apparatus by withdrawing therefrom the generated permanent gases, substantially free of condensable components while maintaining the oil body at decomposition temperatures and retaining the condensible component in the vapor space of theapparatus.

6. A process of converting. hydrocarbon oil which comprises heating a bodyof relatively heavy oil in an enlarged chamber to a'cracking temperature under the pressure of incondensible gases andisubstantially all of the condensible vapors'evolved from the oil during theprocess, maintainingsuch tem- 1 perature for a suflicient time to effect a sub stantial conversion of the-oil into lighter hydrocarbons, regulatingthe pressure on the 'oil during conversion by discharging incondensible gases and incondensible vapors from said enlarged chamber to a condenser, returning all the condensible vapors as condensate to the body of oil and conveying away the incondensible gases, separately discharging liquid products of conversion from said enlarged chamber and subjecting the liquid products so discharged to distillation.

7. A process of converting hydrocarbon oil which comprises heating and digesting the oil in a coil and enlarged chamber, a body of liquid oil being maintained in the enlarged chamber under the pressure of incondensible gases and substantially all of the condensible vapors evolved from the oil during the process and the enlarged chamber being situated outside of the heating zone, withdrawing incondensible gaseous and incondensible vaporous products of conversion from the upper portion of said chamber, subjecting the same to a condensing action, returning all the condensible vaporous products as condensate to the body of oil and reheating the same to produce further cracking therein, conveying away the incondensible gaseous products, separately discharging liquid products of conversion from said enlarged chamber and subjecting the liquid products so discharged to distillation.

8. A process of converting hydrocarbon oil which comprises heating and digesting the oil in a coil and enlarged chamber, a body of liquid oil being maintained in the enlarged chamber under the pressure of incondensible gases and substantially all of the condensible vapors evolved from the oil during the process and the enlarged chamber being situated outside of the heating zone, withdrawing incondensible gaseous and incondensible vaporous products of conversion from the upper portion of said chamber and subjecting the same to a condensing action, returning all the condensible vaporous products as condensate to the body of oil and conveying away the incondensible gaseous products, separately discharging from the said enlarged chamber liquid products of conversion containing substantial amounts of the constituents of gasoline and separating gasoline therefrom.

9. A process of converting hydrocarbon oil which comprises heating a body of oil to .a, cracking temperature under pressilre of the gases and vapors evolved from the oil, maintaining such temperature for :a sufficient time to efieet a substantial conversion oftIhe oil into lighter hydrocarbons, and regulating the pressure on the oil during conversion by releasing permanent gases substantially free from condensable components from thempor space above the oil through a reflux condenser, and passing all the condensate from said reflux condenser only to the oil body.

In testimony whereof, I have signed my name to this specification this 14th day of March, 1927.

WALTER GROSS.

CERTIFICATE OF CORRECTION.

Patent No. 1,847,082. March 1, 1932.

WALTER M. CROSS.

lt is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, line 37, for "geases" read gases, and lines 4]. and 42, for "residuum" read residuums; page 3, lines 80, 97 and US, claims 6, 7 and 8, respectively, for "incondensible" read condensible; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 12th day of July, A. D. 1932.

M. J. Moore, (Seal) Acting Commissioner of Patents. 

